Synthesis and Reactivity of the Unsaturated Trinuclear Phosphanido Complex [(C6F5)2Pt(渭-PPh2)2Pt(渭-PPh2)2Pt(PPh3

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• 作者：Juan Forni茅s ; Consuelo Fortu帽o ; Susana Ib谩帽ez ; Antonio Mart铆n ; Piero Mastrorilli ; Vito Gallo ; Athanassios Tsipis
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：February 18, 2013
• 年：2013
• 卷：52
• 期：4
• 页码：1942-1953
• 全文大小：863K
• 年卷期：v.52,no.4(February 18, 2013)
• ISSN：1520-510X

文摘

The reaction of [NBu₄][(C₆F₅)₂Pt(渭-PPh₂)₂Pt(渭-PPh₂)₂Pt(O,O-acac)] (48 VEC) with [HPPh₃][ClO₄] gives the 46 VEC unsaturated [(C₆F₅)₂Pt¹(渭-PPh₂)₂Pt²(渭-PPh₂)₂Pt³(PPh₃)](Pt²鈥揚t³) (1), a trinuclear compound endowed with a Pt鈥揚t bond. This compound displays amphiphilic behavior and reacts easily with nucleophiles L, yielding the saturated complexes [(C₆F₅)₂Pt^II(渭-PPh₂)₂Pt^II(渭-PPh₂)₂Pt^II(PPh₃)L] [L = PPh₃ (2), py (3)]. The reaction with the electrophile [Ag(OClO₃)PPh₃] affords the adduct 1路AgPPh₃, which evolves, even at low temperature, to a mixture in which [(C₆F₅)₂Pt^III(渭-PPh₂)₂Pt^III(渭-PPh₂)₂Pt^II(PPh₃)₂]²⁺(Pt^III鈥揚t^III) and 2 (plus silver metal) are present. The nucleophilic nature of 1 is also demonstrated through its reaction with cis-[Pt(C₆F₅)₂(THF)₂], which results in the formation of [Pt₄(渭-PPh₂)₄(C₆F₅)₄(PPh₃)] (4). The structure and NMR features indicate that 1 can be better considered as a Pt^II鈥揚t^III鈥揚t^I complex instead of a Pt^II鈥揚t^II鈥揚t^II derivative. Theoretical calculations (density functional theory) on similar model compounds are in agreement with the assigned oxidation states of the metal centers. The strong intermetallic interactions resulting in a Pt²鈥揚t³ metal鈥搈etal bond and the respective bonding mechanism were verified by employing a multitude of computational techniques (natural bond order analysis, the Laplacian of the electron density, and localized orbital locator profiles).